Abstract
In response to the high cost of activated persulfate technology, we have successfully prepared a composite catalyst N-rGO/Fe3O4 for reuse through magnetic separation. The degradation efficiency of 60 mg/L tetracycline (TC) reached 100% within 120 min under optimal conditions (c[peroxysulfate, PDS] = 2 mM; m(PDS):m(N-rGO/Fe3O4) = 1:6; pH = 3.0), while N-rGO/Fe3O4 maintained a high stability and reusability value in the cycling experiment. We found that in the N-rGO/Fe3O4 + PDS system, SO4−· and ·OH radicals were the most dominant reactants for TC decomposition, with non-radical reactions also contributing to TC degradation. Furthermore, we inferred four possible decomposition pathways of TC from the analysis of intermediates: (1) dehydration, (2) demethylation, (3) hydroxylation, and (4) deamidation. This study provides a new strategy for the effective treatment of antibiotic wastewater and hopes to be applied to the treatment of actual antibiotic wastewater in the future.
Graphical Abstract
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
Data Availability
All data, models, and code generated or used during the study appear in the submitted article.
References
Amiri, M. J., Faraji, A., Azizi, M., Nejad, B. G., & Arshadi, M. (2021). Recycling bone waste and cobalt-wastewater into a highly stable and efficient activator of peroxymonosulfate for dye and HEPES degradation. Process Safety and Environmental Protection, 147, 626–641. https://doi.org/10.1016/j.psep.2020.12.039
Amiri, M. J., Afshari, M., Dinari, M., & Arshadi, M. (2022). Activation of peroxymonosulfate by Fe0 for the degradation of BTEX: Effects of aging time and interfering ions. Sustainability, 14(22), 15247. https://doi.org/10.3390/su142215247
Amor, C., Rodríguez-Chueca, J., Fernandes, J. L., Dominguez, J. R., Lucas, M. S., & Peres, J. A. (2019). Winery wastewater treatment by sulphate radical based-advanced oxidation processes (SR-AOP): Thermally vs UV-assisted persulphate activation. Process Safety and Environmental Protection, 122, 94–101. https://doi.org/10.1016/j.psep.2018.11.016
Bi, W., Wu, Y., Wang, X., Zhai, P., & Dong, W. (2016). Degradation of oxytetracycline with SO4- under simulated solar light. Chemical Engineering Journal, 302, 811–818. https://doi.org/10.1016/j.cej.2016.05.075
Chen, W., & Huang, C. (2015). Mineralization of aniline in aqueous solution by electro-activated persulfate oxidation enhanced with ultrasound. Chemical Engineering Journal, 266, 279–288. https://doi.org/10.1016/j.cej.2014.12.100
Chen, C., & Zheng, Y. (2015). Degradation of oxytetracycline in wastewater by multi-frequency ultrasonic. Chemical Industry and Engineering Progress, 34(4), 1143–1146. https://doi.org/10.16085/j.issn.1000-6613.2015.04.042
Chen, Y., Ma, Y., Yang, J., Wang, L., Lv, J., & Ren, C. (2017). Aqueous tetracycline degradation by H2O2 alone: Removal and transformation pathway. Chemical Engineering Journal, 37(1), 15–23. https://doi.org/10.1016/j.cej.2016.08.046
Chen, L., Zuo, X., Zhou, L., Huang, Y., Yang, S., Cai, T., & Ding, D. (2018). Efficient heterogeneous activation of peroxymonosulfate by facilely prepared Co/Fe bimetallic oxides: Kinetics and mechanism. Chemical Engineering Journal, 345, 364–374. https://doi.org/10.1016/j.cej.2018.03.169
Chen, J., Chu, K., Sun, S., Chen, H., Song, B., Wang, J., Liu, Z., & Zhu, L. (2023). Synthesis of magnetic core-shell Fe3O4-Mn3O4 composite for degradation of sulfadiazine via peroxymonosulfate activation: Characterization, mechanism and toxicity analysis. Journal of Environmental Chemical Engineering, 11(1), 109230. https://doi.org/10.1016/j.jece.2022.109230
Cui, Q., Zhang, W., Chai, S., Zuo, Q., & Kim, K. (2022). The potential of green biochar generated from biogas residue as a heterogeneous persulfate activator and its non-radical degradation pathways: Adsorption and degradation of tetracycline. Environmental Research, 204, 112335. https://doi.org/10.1016/j.envres.2021.112335
Ding, Y., Zhu, L., Wang, N., & Tang, H. (2013). Sulfate radicals induced degradation of tetrabromobisphenol A with nanoscaled magnetic CuFe2O4 as a heterogeneous catalyst of peroxymonosulfate. Applied Catalysis b: Environmental, 129, 153–162. https://doi.org/10.1016/j.apcatb.2012.09.015
Ding, D., Liu, C., Ji, Y., Yang, Q., Chen, L., Jiang, C., & Cai, T. (2017). Mechanism insight of degradation of norfloxacin by magnetite nanoparticles activated persulfate: Identification of radicals and degradation pathway. Chemical Engineering Journal, 308, 330–339. https://doi.org/10.1016/j.cej.2016.09.077
Duan, X., Sun, H., Tade, M., & Wang, S. (2018). Metal-free activation of persulfate by cubic mesoporous carbons for catalytic oxidation via radical and nonradical processes. Catalysis Today, 307, 140–146. https://doi.org/10.1016/j.cattod.2017.04.038
Gu, H., Lang, J., Ma, Y., Gu, H., Song, Y., Chai, Z., Li, G., &Wang, X. (2018). Phosphotungstic acid binding in situ to K4Nb6O17 for the effective adsorption-photocatalytic removal of tetracycline. Journal Of Nanoparticle Research, 132(20). https://doi.org/10.1007/s11051-018-4229-z
Hou, L., Zhang, Q., Jérôme, F., Duprez, D., Zhang, H., & Royer, S. (2014). Shape-controlled nanostructured magnetite-type materials as highly efficient Fenton catalysts. Applied Catalysis b: Environmental, 144, 739–749. https://doi.org/10.1016/j.apcatb.2013.07.072
Ji, L., Wan, Y., Zheng, S., & Zhu, D. (2011). Adsorption of tetracycline and sulfamethoxazole on crop residue-derived ashes: Implication for the relative importance of black carbon to soil sorption. Environmental Science & Technology, 13(45), 5580.
Ji, Y., Ferronato, C., Salvador, A., Yang, X., & Chovelon, J. (2014). Degradation of ciprofloxacin and sulfamethoxazole by ferrous-activated persulfate: Implications for remediation of groundwater contaminated by antibiotics. Science of the Total Environment, 472, 800–808. https://doi.org/10.1016/j.scitotenv.2013.11.008
Ji, Y., Shi, Y., Dong, W., Wen, X., Jiang, M., & Lu, J. (2016). Thermo-activated persulfate oxidation system for tetracycline antibiotics degradation in aqueous solution. Chemical Engineering Journal, 298, 225–233. https://doi.org/10.1016/j.cej.2016.04.028
Jia, Y., Wen, Y., Han, X., Qi, J., Liu, Z., Zhang, S., & Li, G. (2018). Electrocatalytic degradation of rice straw lignin in alkaline solution through oxidation on a Ti/SnO2-Sb2O3/-PbO2/-PbO2 anode and reduction on an iron or tin doped titanium cathode. Catalysis Science & Technology, 8(18), 4665–4677. https://doi.org/10.1039/x0xx00000x
Kakavandi, B., Takdastan, A., Pourfadakari, S., Ahmadmoazzam, M., & Jorfi, S. (2019). Heterogeneous catalytic degradation of organic compounds using nanoscale zero-valent iron supported on kaolinite: Mechanism, kinetic and feasibility studies. Journal of the Taiwan Institute of Chemical Engineers, 96, 329–340. https://doi.org/10.1016/j.jtice.2018.11.027
Kaur, B., Kuntus, L., Tikker, P., Kattel, E., Trapido, M., & Dulova, N. (2019). Photo-induced oxidation of ceftriaxone by persulfate in the presence of iron oxides. Science of the Total Environment, 676, 165–175. https://doi.org/10.1016/j.scitotenv.2019.04.277
Kermani, M., Mehralipour, J., & Kakavandi, B. (2019). Photo-assisted electroperoxone of 2,4-dichlorophenoxy acetic acid herbicide: Kinetic, synergistic and optimization by response surface methodology. Journal of Water Process Engineering, 32, 100971. https://doi.org/10.1016/j.jwpe.2019.100971
Lee, H., Lee, C., & Kim, J. (2016). Response to comment on “Activation of persulfate by graphitized nanodiamonds for removal of organic compounds.” Environmental Science & Technology, 18(50), 10134. https://doi.org/10.1021/acs.est.7b01642
Li, S., Li, X., & Wang, D. (2004). Membrane (RO-UF) filtration for antibiotic wastewater treatment and recovery of antibiotics. Separation and Purification Technology, 34(1), 109–114. https://doi.org/10.1016/S1383-5866(03)00184-9
Li, S., Guo, R., Li, B., Liang, Y., Wang, Z., & Qu, R. (2023). Kinetics and mechanism studies of efficient degradation of 1-hexyl-3-methylimidazolium by zero-valent iron activated persulfate. Chemical Engineering Journal, 460, 141575. https://doi.org/10.1016/j.cej.2023.141575
Li, X., Wang, J., Xia, L., Cheng, R., Chen, J., & Shang, J. (2023). Peroxymonosulfate activation by nitrogen-doped herb residue biochar for the degradation of tetracycline. Journal of Environmental Management, 328, 117028. https://doi.org/10.1016/j.jenvman.2022.117028
Liu, H., Sun, P., Feng, M., Liu, H., Yang, S., Wang, L., & Wang, Z. (2016). Nitrogen and sulfur co-doped CNT-COOH as an efficient metal-free catalyst for the degradation of UV filter BP-4 based on sulfate radicals. Applied Catalysis b: Environmental, 187, 1–10. https://doi.org/10.1016/j.apcatb.2016.01.036
Lyu, H., Li, P., Tang, J., Zou, W., Wang, P., Gao, B., & Dong, L. (2023). Single-atom Mn anchored on N-doped graphene oxide for efficient adsorption-photocatalytic degradation of sulfanilamide in water: Electronic interaction and mineralization pathway. Chemical Engineering Journal, 454, 140120. https://doi.org/10.1016/j.cej.2022.140120
Manda, A. A., Haladu, S. A., Elsayed, K. A., Ibrahim Gaya, U., Alheshibri, M., Al Baroot, A., Çevik, E., Ercan, O., Ercan, F., Kayed, T. S., Musa Magami, S., & Altamimi, N. A. (2023). Fast one-pot laser-based fabrication of ZnO/TiO2-reduced graphene oxide nanocomposite for photocatalytic applications. Optics & Laser Technology, 160, 109105. https://doi.org/10.1016/j.optlastec.2022.109105
Martucci, A., Cremonini, M. A., Blasioli, S., Gigli, L., Gatti, G., Marchese, L., & Braschi, I. (2013). Adsorption and reaction of sulfachloropyridazine sulfonamide antibiotic on a high silica mordenite: A structural and spectroscopic combined study. Microporous and Mesoporous Materials, 170, 274–286. https://doi.org/10.1016/j.micromeso.2012.11.031
Noorisepehr, M., Kakavandi, B., Isari, A. A., Ghanbari, F., Dehghanifard, E., Ghomi, N., & Kamrani, F. (2020). Sulfate radical-based oxidative degradation of acetaminophen over an efficient hybrid system: Peroxydisulfate decomposed by ferroferric oxide nanocatalyst anchored on activated carbon and UV light. Separation and Purification Technology, 250, 116950. https://doi.org/10.1016/j.seppur.2020.116950
Olmez-Hanci, T., Arslan-Alaton, I., & Genc, B. (2013). Bisphenol A treatment by the hot persulfate process: Oxidation products and acute toxicity. Journal of Hazardous Materials, 263, 283–290. https://doi.org/10.1016/j.jhazmat.2013.01.032
Pan, X., Chen, J., Wu, N., Qi, Y., Xu, X., Ge, J., Wang, X., Li, C., Qu, R., Sharma, V. K., & Wang, Z. (2018). Degradation of aqueous 2,4,4′-trihydroxybenzophenone by persulfate activated with nitrogen doped carbonaceous materials and the formation of dimer products. Water Research, 143, 176–187. https://doi.org/10.1016/j.watres.2018.06.038
Pan, Y., Peng, Z., Liu, Z., Shao, B., Liang, Q., He, Q., Wu, T., Zhang, X., Zhao, C., Liu, Y., Ge, L., & He, M. (2022). Activation of peroxydisulfate by bimetal modified peanut hull-derived porous biochar for the degradation of tetracycline in aqueous solution. Journal of Environmental Chemical Engineering, 10(2), 107366. https://doi.org/10.1016/j.jece.2022.107366
Peng, G., Zhang, M., Deng, S., Shan, D., He, Q., & Yu, G. (2018). Adsorption and catalytic oxidation of pharmaceuticals by nitrogen-doped reduced graphene oxide/Fe3O4 nanocomposite. Chemical Engineering Journal, 341, 361–370. https://doi.org/10.1016/j.cej.2018.02.064
Pu, M., Guan, Z., Ma, Y., Wan, J., Wang, Y., Brusseau, M. L., & Chi, H. (2018). Synthesis of iron-based metal-organic framework MIL-53 as an efficient catalyst to activate persulfate for the degradation of orange G in aqueous solution. Applied Catalysis a: General, 549, 82–92. https://doi.org/10.1016/j.apcata.2017.09.021
Qi, C., Liu, X., Li, Y., Lin, C., Ma, J., Li, X., & Zhang, H. (2017). Enhanced degradation of organic contaminants in water by peroxydisulfate coupled with bisulfite. Journal of Hazardous Materials, 328, 98–107. https://doi.org/10.1016/j.jhazmat.2017.01.010
Sable, S. S., Shah, K. J., Chiang, P., & Lo, S. (2018). Catalytic oxidative degradation of phenol using iron oxide promoted sulfonated-ZrO2 by advanced oxidation processes (AOPs). Journal of the Taiwan Institute of Chemical Engineers, 91, 434–440. https://doi.org/10.1016/j.jtice.2018.06.030
Sassman, S., & Lee, L. (2005). Sorption of three tetracyclines by several soils: Assessing the role of pH and cation exchange. Environmental Science & Technology, 39(19), 7452–7459. https://doi.org/10.1021/es0480217
Sharma, G., Kumar, A., Naushad, M., Kumar, A., Al-Muhtaseb, A. H., Dhiman, P., Ghfar, A. A., Stadler, F. J., & Khan, M. R. (2018). Photoremediation of toxic dye from aqueous environment using monometallic and bimetallic quantum dots based nanocomposites. Journal of Cleaner Production, 172, 2919–2930. https://doi.org/10.1016/j.jclepro.2017.11.122
Sun, H., Wang, Y., Liu, S., Ge, L., Wang, L., Zhu, Z., & Wang, S. (2013). Facile synthesis of nitrogen doped reduced graphene oxide as a superior metal-free catalyst for oxidation. Chemical Communications, 49, 9914–9916. https://doi.org/10.1039/c3cc43401j
Wang, X., Li, X., Zhang, L., Yoon, Y., Weber, P. K., Wang, H., Guo, J., & Dai, H. (2009). N-doping of graphene through electrothermal reactions with ammonia. Science, 324, 768–771. https://doi.org/10.1126/science.1170335
Wang, X., Qin, Y., Zhu, L., & Tang, H. (2015). Nitrogen-doped reduced graphene oxide as a bifunctional material for removing bisphenols: Synergistic effect between adsorption and catalysis. Environmental Science & Technology, 49(11), 6855–6864. https://doi.org/10.1021/acs.est.5b01059
Wang, J., Zhi, D., Zhou, H., He, X., & Zhang, D. (2018). Evaluating tetracycline degradation pathway and intermediate toxicity during the electrochemical oxidation over a Ti/Ti4O7 anode. Water Research, 137, 324–334. https://doi.org/10.1016/j.watres.2018.03.030
Wang, Y., Wang, C., Yan, S., Li, Y., Cai, C., Liu, H., Ren, P., Wang, M., & Kuang, S. (2023). The removal of antibiotic, antibiotic resistant bacteria and genes in persulfate oxidation system via activating by antibiotic fermentation dregs derived biochar. Journal of Cleaner Production, 394, 136328. https://doi.org/10.1016/j.jclepro.2023.136328
Wang, M., Wang, Y., Li, Y., Wang, C., Kuang, S., Ren, P. & Xie, B. (2023a). Persulfate oxidation of tetracycline, antibiotic resistant bacteria, and resistance genes activated by Fe doped biochar catalysts: Synergy of radical and non-radical processes. Chemical Engineering Journal, 142558. https://doi.org/10.1016/j.cej.2023.142558
Wu, J., Bai, J., Wang, Z., Liu, Z., Mao, Y., Liu, B., & Zhu, X. (2020). UV-assisted nitrogen-doped reduced graphene oxide/Fe3O4 composite activated peroxodisulfate degradation of norfloxacin. Environmental Technology, 43(7), 1–15. https://doi.org/10.1080/09593330.2020.1779353
Yan, J., Lei, M., Zhu, L., Anjum, M. N., Zou, J., & Tang, H. (2011). Degradation of sulfamonomethoxine with Fe3O4 magnetic nanoparticles as heterogeneous activator of persulfate. Journal of Hazardous Materials, 186(2), 1398–1404. https://doi.org/10.1016/j.jhazmat.2010.12.017
Yuan, Q., Guo, M., Wei, W., & Yang, J. (2016). Reductions of bacterial antibiotic resistance through five biological treatment processes treated municipal wastewater. Environmental Science & Pollution Research, 19(23), 1–9.
Zhu, X., Wang, Y., Sun, R., & Zhou, D. (2013). Photocatalytic degradation of tetracycline in aqueous solution by nanosized TiO2. Chemosphere, 92(8), 925–932. https://doi.org/10.1016/j.chemosphere.2013.02.066
Funding
The authors acknowledge Science and Technology Project of Henan Province (Grant No. 232102320132), Key projects of Education Department of Henan Province (Grant No. 21B610002), supported by Natural Science Foundation of Henan (No. 222300420106).
Author information
Authors and Affiliations
Corresponding authors
Ethics declarations
Conflict of Interest
The authors declare no competing interests.
Additional information
Publisher's Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Rights and permissions
Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.
About this article
Cite this article
Bai, J., Wang, L., Wu, J. et al. Peroxydisulfate Activation for Efficient Degradation of Tetracycline by N-rGO/Fe3O4: Synthesis, Property, and Mechanism. Water Air Soil Pollut 234, 399 (2023). https://doi.org/10.1007/s11270-023-06376-8
Received:
Accepted:
Published:
DOI: https://doi.org/10.1007/s11270-023-06376-8